![Page 1: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/1.jpg)
Adsorption/Desorption of Pollutants to Nanoparticles
Mason Tomson, V. L. ColvinXuekun Cheng, Y. Gao, R. Wahi, A. T. Kan
Center for Biological and Environmental NanotechnologyCivil and Environmental Engineering and Chemistry
DepartmentsRice University
September 15, 2003
![Page 2: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/2.jpg)
Adsorption/Desorption Hysteresis
Reaction Uptake
BiodegradationVolatilization
DesorptionToxicity
![Page 3: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/3.jpg)
Black Carbon
![Page 4: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/4.jpg)
Sorption/Desorption HysteresisdespK
adspK>
0.00.51.01.52.02.5
Solid
Pha
seC
onc
(µg/
g)
0.0 0.2 0.5 0.8 1.0
Solution Phase Conc (µg/ml)
Naphthalene/LulaDesorption
Adsorption
![Page 5: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/5.jpg)
Rev. Irr.
max
max
Water
~0.01
102030
0.02 (µg/
ml)
(µg/
g)
"Unweathered,non-remediated, or freshly
contaminated"
"Weathered,remediated, or aged"
Sediment
Rev. Irr.1 02 0
4 05 06 0
3 0
max
max
Rev.
~
Water
0.01
102030
0.02
Irr.
1020
405060
30
Irr.Rev.
Sediment
(µg/
ml)
(µg/
g)
![Page 6: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/6.jpg)
Adsorption/Desorption Hysteresis
0.1
10
103
105
10-7 10-5 0.1 10 1000Solution Phase Conc (mg/L)
102
105
104
103
106
K OC=10
7 Boston Harbor:1. Phenanthrene2. Pyrene3. Cl 5-PCB4. Cl 6-PCB
Lake Charles, LA :5. Cl 2-Benzene6. Cl 3-Benzene7. Cl 4-Benzene8. Cl 6-Benzene9. Cl 6-Butadiene
Example:MCL (WQC) forp-Cl 2-Benzene withKoc ~1000So
lid P
hase
Con
c(m
g/K
g -O
C)
AqueousSolubility (mg/L)
IrreversibleSQC
ReversibleSQC
10-3
Tolu
ene
Phen
Nap
h
PCE
TCE
Ben
DD
TC
l 6-B
en
Cl 2-
Ben
Cl 4-
Ben
Cl 6-
But
Cl 2-
PCB
Cl 4-
PCB
![Page 7: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/7.jpg)
Naphthalene Adsorption onto Original C60 Particles
E. Ballesteros et al. 2000 J. Chromatography A —
Little adsorption from naphthalene aqueous solution onto fullerene C60 particles was found...
Kp ~ 10
Flow In:Naphthalene
0.1ug/mlFlow Out:
Naphthalene
22% Naphthalene adsorbed
Fullerene C60Column
![Page 8: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/8.jpg)
Carbon Nano-Particle Transport
C60 smallaggregates
Toluene extraction
C60 colloidalparticles
TolueneNo extraction
C-18 Sep-Pak®
No adsorption
![Page 9: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/9.jpg)
Adsorption of Organic Contaminants from Solution to C60 Fullerene
Batch Adsorption/Desorption Study:
C60 largeaggregates
C60 smallaggregates
C60 colloidalparticles
![Page 10: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/10.jpg)
UV/Vis Spectrum of C60 in TolueneSampled from small aggregates
407nm
424nm690nm
![Page 11: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/11.jpg)
Naphthalene-Carbon Adsorption Isotherms
(1) Activated carbon (2) Large aggregatesq=105.20C0.31
0
200
400
600
800
1000
0 1 2 3 4
Solution Phase C (ug/ml)
Solid
Pha
se C
(ug/
g)
q=102.39C
(3) Colloidal C60
020000400006000080000
100000120000
0 0.1 0.2 0.3Solution Phase C (ug/ml)
Solid
Pha
se C
(ug/
g)
(3) Small aggregates
02000400060008000
100001200014000
0 0.1 0.2 0.3 0.4Soultion Phase C (ug/ml)
Solid
Pha
se C
(ug/
g)
q=104.27C0.44
0
5000
10000
15000
0 1 2 3Solution Phase Conc. (mg/ml)
Solid
Phas
e Con
c. (m
g/g)
q=103.75C
![Page 12: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/12.jpg)
Adsorption/Desorption of Naphthalene(Small Aggregated and Colloidal C60 Particles)
0
2000
4000
6000
8000
10000
12000
0 0.1 0.2 0.3 0.4Solution Phase Conc. (mg/ml)
Solid
Pha
se C
onc.
( m
g/g)
Adsorption
0
2000
4000
6000
8000
10000
12000
14000
0 1 2 3
Solution Phase Conc. (mg/ml)
Solid
Pha
se C
onc.
(mg/
g)
Adsorption
DesorptionDesorption
Small aggregates Colloidal C60
![Page 13: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/13.jpg)
Adsorption/Desorption of Naphthalene to Small Aggregated C60 Particles
00.050.1
0.150.2
0.250.3
0.35
0 10 20 30 40 50 60 70Desorption Time(d)
Solu
tion
Phas
e C
(ug/
ml)
0%
2%
4%
6%
8%
10%
12%
0 10 20 30 40 50 60 70Desorption Time(d)
% D
esor
bed
#1#3
![Page 14: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/14.jpg)
Adsorption and Desorption of Organic Contaminants
102
105
104
103
106
K oc= 10
7
Solid
Pha
se C
onc.
(mg/
Kg
-OC
)
0.1
10
103
105
10-7 10-5 0.1 10 1000Solution Phase Conc. (mg/L)
Boston Harbor:1. Phenanthrene2. Pyrene3. Cl5-PCB4. Cl6-PCB
Lake Charles, LA:5. Cl2-Benzene6. Cl3-Benzene7. Cl4-Benzene8. Cl6-Benzene9. Cl6-Butadiene
Phen
Cl 2-
PCB
Nap
hC
l 2-B
enPC
ETo
luen
eTC
EB
en
DD
TC
l 6-B
enC
l 4-PC
B
Cl 6-
But
Cl 4-
Ben
Example:MCL (WQC) forp-Cl2-Benzene withKoc ~1000
AqueousSolubility (mg/L)
IrreversibleSQC
ReversibleSQC
10-3
Naturally occurringsoil organic carbon
10-7 10-5 10-3 0.1 10 1000
ads
des
Naphthalene
C60 Fullerene 105
103
10
0.1
Solution Phase Conc. (µg/ml)
Solid
pha
se c
onc.
(µg/
g)
Solid Lines Represent the Rice University Dual Equilibrium Model
![Page 15: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/15.jpg)
Carbon Nano-Particle Transport
C60 smallaggregates
Toluene extraction
C60 colloidalparticles
TolueneNo extraction
C-18 Sep-Pak®
No adsorption
![Page 16: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/16.jpg)
What Happened During Adsorption?
Naphthalene
adsorption aggregation
Clusters Aggregation &
Naph. Entrapment
Small Fullerene Aggregates
Naphthalene Adsorption
![Page 17: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/17.jpg)
What Happened During Desorption?
“Loosely” Adsorbed
Naphthalene
desorption
“Entrapped”Naphthalene
![Page 18: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/18.jpg)
Possible Explanations
Two parts of adsorption/desorption:
q1: adsorption onto surfaces
q2: entrapment in clusters
q1 account for ≈ 11% adsorption;
q2 account for ≈ 89% adsorption
Possibility of adsorption/desorption hysteresis
Adsorption/desorption hysteresis needs further study
![Page 19: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/19.jpg)
Adsorption of Cadmium to Anatase Nanoparticles
![Page 20: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/20.jpg)
Adsorption/Desorption of Cd to Soil
01234567
0 0.05 0.1Solution Phase Cd Conc.
(mmol/L)
Solid
Cd
Con
c. (m
mol
/kg)
0102030405060708090
100
3 4 5 6 7 8
pH
% C
d ad
s or
des
Reversible Irreversible
AdsDes
![Page 21: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/21.jpg)
Physical Characteristics of Anatase
Sample CrystallinePhases Detectedby XRD
Specific SurfaceArea, (m2/g)
Mean ParticleSize (nm)
AmorphousTiO2 Detectedby TG/DTA
Sigma Anatase 10.8 145 noneAlfa Aesar Anatase 11.2 139.5 noneTiNano Anatase 39.8 39.2 noneP-25 Anatase (80%),
rutile (20%)46.9 33.3 none
RHT 47 Anatase 75.1 20.8 noneRHT 24 Anatase 108.5 14.4 --RHT 45 Anatase -- 9.45 --
RHT 43 Anatase -- 7.72 --
RHT 69 Anatase 195.3 8.0 noneRHT 127 Anatase 193.4 8.08 none
![Page 22: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/22.jpg)
TEM Images of Anatase
Large CrystalsNanoparticles (RHT-69)
100 nm20 nm
![Page 23: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/23.jpg)
Adsorption of Cadmium to Large and Nano-Anatase
20 nm
0
1
2
3
4
0.0 0.5 1.0
C (mmol/ml)
q (m
mol
/m2)
Nanoparticles
100 nm
01234
0.0 0.5 1.0C (mmol/ml)
q (m
mol
/m2)
Large crystals
![Page 24: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/24.jpg)
Langmuir Adsorption Isotherm Parameters
Solid Qmax
(µmol/m2)
b
(ml/µmol)
Qmax·b
(ml/m2)
σQºc
(ml/m2)
σbc
(ml/µmol)
Rc
Sigma andAlfa Aesara
3.19 108.7 346.75 0.12 29.2 0.978
P-25 andTiNanob
3.50 3.70 12.94 0.10 0.40 0.985
RHT-47 3.25 8.94 29.02 0.15 1.33 0.991
RHT 69 2.55 7.71 19.7 0.12 1.06 0.991
![Page 25: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/25.jpg)
Adsorption/Desorption Reversibility
050
100150200250300350400
0 0.1 0.2 0.3 0.4 0.5
Cd in solution (mmol/l)
Cd
ads
(mm
ol/k
g)RHT 69
Nanoparticles
0
5
10
15
20
25
30
0 0.04 0.08 0.12
Cd in solution (mmol/l)
Cd
ads (
mm
ol/k
g)
Large Crystals
Sigma
![Page 26: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/26.jpg)
Electrochemical Propertiesg of solid added Initial
pHFinalpH 2m
pH∆
0.8g Sigma Anatase 7.50 6.59 0.1050.2g Tinano 40 7.51 6.61 0.1132.0g Sigma Anatase 7.30 6.37 0.0430.5g Tinano 40 7.32 6.33 0.050
0.8g Sigma Anatase 6.03 5.99 0.0020.2g Tinano 40 6.02 5.92 0.0072.0g Sigma Anatase 6.01 5.97 0.0050.5g Tinano 40 6.00 5.86 0.012Reported pzc: 5.8 - 6.1 pH
![Page 27: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/27.jpg)
Surface Charges and pH Adsorption Edge
-0.25
-0.15
-0.05
0.05
0.15
0.25
3.5 4.5 5.5 6.5 7.5pH of Suspension
σ (C
/m2
solid
) TiNanoSigma
Potential Titration TiO2 suspension
0
20
40
60
80
100
3 4 5 6 7 8 9 10
pH of Solution
% C
d ad
sorp
tion
SigmaTiNano
Cd adsorption vs. pH
![Page 28: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/28.jpg)
Summary
States of aggregation of nanoparticles may change in various aqueous environmentAdsorption of contaminants to the surfaces of nanoparticles is very strongAdsorption/desorption of organic compounds to nanoparticles might be hystereticAdsorption/desorption of heavy metals onto/from nanoparticles are predictable based on surface area normalized sorption isothermNanomaterials in natural aqueous environments may affect the fate and transport of contaminants substantially
![Page 29: Adsorption/Desorption of Pollutants to Nanoparticles · 2015. 9. 18. · Adsorption/Desorption Hysteresis 0.1 10 103 105 10-7 10-5 0.1 10 1000 Solution Phase Conc (mg/L) 10 6 10 5](https://reader036.vdocuments.site/reader036/viewer/2022071417/61153e4bd7244824766ca356/html5/thumbnails/29.jpg)
Future
Responsible UseRemediation